Ethyl bromoacetate → 3-Cyano-3-(3,4-dimethylphenyl)pentanedioic acid diethyl ester

HRID 343534

Reaction equation

HRID 343534 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH3:11][C:12]1[CH:13]=[C:14]([CH2:19][C:20]#[N:21])[CH:15]=[CH:16][C:17]=1[CH3:18].Br[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]>O1CCCC1.C(OCC)C>[CH2:27]([O:26][C:24](=[O:25])[CH2:23][C:19]([C:20]#[N:21])([C:14]1[CH:15]=[CH:16][C:17]([CH3:18])=[C:12]([CH3:11])[CH:13]=1)[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH3:28]

Participants

6

Reactant 3

HCID 7748Ethyl bromoacetateHCID 764012-(3,4-Dimethylphenyl)acetonitrileHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 538454283-Cyano-3-(3,4-dimethylphenyl)pentanedioic acid diethyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Cool a solution of sodium bis(trimethylsilyl)amide (723 mL, 1M in tetrahydrofuran, 723 mmol) to 0° C. in an ice bath. Add a solution of 3,4-dimethylphenylacetonitrile (50.0 mmol) in tetrahydrofuran (130 mL) over about 1.5 hours. When the addition is complete, warm the reaction mixture to ambient temperature and allow to stir. After 2 hours, transfer the above solution via cannula into a cooled (-50° C.) solution of ethyl bromoacetate (126 g, 757 mmol) in tetrahydrofuran (250 mL). After the transfer is complete, allow the reaction mixture to warm to ambient temperature. After 18 hours, dilute with diethyl ether (500 mL) and extract with water, 1M hydrochloric acid solution, saturated aqueous solution of sodium bicarbonate, and then brine. Dry the organic layer over MgSO4, filter, and concentrate in vacuo to give a residue. Recrystallize the residue from diethyl ether to give the title compound as a solid.

Workup

  1. additionWhen the addition
  2. temperatureto warm to ambient temperature
  3. waitAfter 18 hours
  4. extractionextract with water, 1M hydrochloric acid solution, saturated aqueous solution of sodium bicarbonate
  5. dry with materialDry the organic layer over MgSO4
  6. filtrationfilter
  7. concentrationconcentrate in vacuo
  8. customto give a residue
  9. customRecrystallize the residue from diethyl ether

Sources & evidence

ORD record
ord-def067296e584bd19a6a2ac04852f922
Source dataset
uspto-grants-1999_01
Patent number
US05861417

Linked notes

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